Preparation of wetting, sudsing, and detergent agents



@atented Feb. 22, 194% PREPARATION OF WET'IING, SUDSING, AND

DETERGENT AGENTS Nathaniel Beverley Tucker,

Glendale, Ohio, as-

signor to The Procter & Gamble Company, Cincinnati,

Ohio, a corporation of Ohio No. Drawing. Application December 29, 1941,

Serial No.

8 Claims. ('01. 260-400) This invention relates to a process for producing highly efiicient sudsing, emulsifying and detergent agents.

More specifically the present case relates to an improved process for the preparation of watersoluble salts of compounds of the following type R -CO -OR1 'SOJOH where R-CO is an acyl radical having eight to twenty-two carbon atoms and R1 is an alkylene or hydroxyalkylene radical having two to four carbon atoms. These salts possess wetting, sudsing and detergent power in hard water and, in accordance with my invention, are produced by the condensation of a salt of a higher fatty acid with a low molecular weight halogen substituted alkyl sulfonate in the presence of formyl morpholine, an amide of formic acid and morpholine having the formula CzHl The present application is related to but distinguishes from my copending application Serial Number 387,985, which concerns a wetting, sudsing ing to which the method for the preparation of and detergent agents accordabove condensation reaction is conducted in the presence of amides volatilizable at a temperature below that at which harmful decomposition products are formed and which have the formula Ra- CO'NRtRt "uct and may be used directly without purification as a washing agent of high eiilciency in hard water if desired.

It is a further object of my invention to provide a means whereby the above compounds' can be manufactured economically and in good yields from soap and halo-alkyl metal sulfonates,

now U. 8. Patent 2,289,391,'

ordinarily such reactions as that of thus making unnecessary the use of the more costly fatty acid halides as starting materials. Other objects of my invention will be apparent iron the following description.

It is known that compounds coming within the classification above given, such as the sodium salt of the oleic acid ester of isethionlc acid (CnHu-CO-OCaHrSOaNa) and the sodium salt of coconut oil fatty acid (predominantly lauric acid) ester of 1,2-dihydroxy propane 3-sulfonic acid (CuHa:-CO0CHz-CHOH-CI-Iz-SOsNa) may be prepared by heating a soap of the fatty acid with a salt of the appropriate halogen substituted sulfonate, by heating the free fatty acid with the hydroxy alkyl sulfonate or by reacting the chloride of the fatty acid with the hydroxy alkyl sulfonate. Since both soap and fatty acids are cheaper reagents than the relatively costly acid chlorides, it is obviously advantageous to use these in preference to the chloride. However, soap with halo-alkyl sulfonate or the reaction of fatty acids with hydroxy alkyl sulfonates progress slowly even at temperatures in the neighborhood of 200 0. Consequently, in prior methods for producing detergent and sudsing agents of the type ,here under consideration from soap or free fatty acid-purification of the resulting product he condensation by crystallization from so]- vents has been necessary for one of two reasons: Either the product contains unreacted harmful .soap because of too short a time of reaction or too low a reaction temperature, or the product contains harmful by-products, including decomposlton products and dark colored materials, because of too long a reaction time or too high a reaction temperature. In either case the imnw ltv i detrimental to the performance of the product as a cleansing agent, and as far as I am aware there is no happy medium in which to operate and obtain an active product resistant to hard water and acid without subjecting the reaction product to expensive and time consuming purification, suitable solvent.

In accordance with the present invention, the

reaction between the soap and the halogen substituted sulfonate is brought nearer theoretical completion by the use of a reaction medium consisting essentially of formyl morpholine, thereby producing a product containing only inconsequential quantities of unreacted soap. In addition, the use of the formyl morpholine reaction medium materially reduces the time and tcmperature of reaction necessary to bring about including crystallization from a however, purification is desired, it may be accomplished easily and readily merely by volatilizing the formyl morpholine under pressure conditions such that temperatures substantially above 175 C. are not required, and separating the formyl morpholine by methods known in the art. Crystallization from a solvent is unnecessary, and attendant disadvantages such as loss of yield and costly operation are therefore avoided.

The highly advantageous action of the formyl morpholine in the preparation of detergents of the type herein referred to is not due solely to any solvent action which the formyl morpholine may have, because I have found that ethylene glycol, which is an excellent solvent for both reactants, does not function in the same manner as the amide used herein, but in contrast thereto results in a lower yield of a reaction product which is contaminated so highly with unreacted soap and other d trimental impurities that purification by crystallization from a solvent is essential in order to obtain an efllclent wetting, sudsing and detergent agent. Apparently the formyl morphollne possesses a characteristic or combination of characteristics such as a catalytic effect in combination with a solvent effect, making this compound especially suitable for the purpose at hand.

In the preferred practice of my invention the fatty acid soap is heated with the halogen substituted sulfonate in the presence of a sufllcient amount of formyl morpholine to effect the formation of a fluid reaction mix at elevated temperature. Under such conditions a substantial part of the reactants is in solution. After the reaction has reached substantial completion, as may be determined for example by titration of a sample of the mix for ionic halogen, the reaction medium may be removed by distillation from the mixture under pressure conditions that permit the use of a temperature below that at which the reactants or products decompose. The residue consists predominantly of the desired detergent product and is sumciently active in sudsing and detergent power that it may be used directly without further purification in washing or laundering operations. Of course purification from a solvent may be eflected if desired.

My invention will be more clearly understoo from the following example in which specific conditions of operation are set forth. However, the invention is not limited to these specific con dltions, as more particularly pointed out hereinafter.

Example-45 parts of dry sodium soap derived from coconut oil are mixed with 39.8 parts monochlorhydrln sulfonate and 100 parts formyl morp oline in a reaction vessel which is not attacked by the reactants, such as a glass-lined vessel for example. The mixture is heated, with stirring, at 140 to 150 C. for two hours, after which most of the formyl morpholine is removed by distillation at 145 C. under vacuum. The product dissolves to a perfectly clear solution in hot or cold hard water and possesses excellent sudsing and detergent characteristics.

In the above example, I have shown how my invention may be practiced with commonly occurring materials. However, while this example may express probably the most practical way of carrying out my process, other materials may be employed. For example, other soaps than coconut oil soap such as oleic acid soap and soaps of other fatty acids individually and in admixture having eight to twenty-two carbon atoms, may be employed. Thus, if desired, the stearates, palmitates or myristates, or soaps from any of the natural occurring vegetable and animal fats and oils may be used. Also, it should be noted that in addition to alkali metal soaps, alkaline earth metal soaps such as calcium and magnesium soaps, or even some heavy metal soaps, may be used provided ithe metal is such that it readily combines with the halogen or the halogen substituted sulfonate to produce a neutral salt, and provided that the metal does not form an insoluble salt with the condensation product.

In the example I have shown the use of a chlorine substituted sulfonate because this derivative is readily available or easily prepared. However, a sulfonate substituted with any other halogen, such as bromine, may be employed with equal case without departing from the spirit of the invention.

The kind of metal ion in the halogen substituted sulfonate salt is relatively unimportant as long a the detergent agent. that is, the condensation product, is water soluble. Thus, for example, the alkali metals sodium and potassium, and the alkaline earth metals calcium and magnesium, may be employed since they form sal which are soluble in hard water. i

The intermediate sulfonates, that is, the halogen substituted sulfonates coming within the scope of the (present invention, are those aliphatic compounds having two to four carbon atoms as above stated. Thus the following compounds, in additionv to the monochlorhydrin sodiumsulfonate given in the example, may be employed: the sodium and potassium beta methyl monochlorhydrln sulfonates, sodium chlorethyl sulionate, salts of chloro olefin sulfonic acids such as 2, chloromethyl propene sodium sulfonate, and others which will be readily apparent to those versed in the art.

The preferred temperature range for conducting the condensation reaction is to C.. but of course the condensation may be carried out at temperatures outside of these limitations. For example, some reaction is evident at temperatures as low as 130 C. and such low temperatures may be fully sufficient in some instances. Of course temperatures higher than 150 C. may also be employed, but temperatures substantially above C. are usually unnecessary and may even be harmful since such high temperatures favor decomposition and the production of undesirable try-products.

The amount of formyl morpholine. which should be empioyed is not very critical. In'my work I have found that amounts as small as one half the weight of the mixture of soap and halogen substituted sulfonate may be employed, but ordinarily I prefer to use an amount of reaction medium which is at least equal to the combined weights of the soap and sulfonate. Of

3. In the process of producing a wetting, suds- Having thus described my invention, what I -claim and desire to secure by Letters Patent is:

1. In the process of producing a wetting, sudsing and detergent agent of the general formula where R-CO is the acyl radical of a fatty acid having eight to twenty-two carbon atoms, R1 is a radical selected from the group consisting of alkylene and hydroxy alkylene radicals having two to four carbon atoms, and Me is a metal forming a water-soluble salt, the step which consists in condensing a metal salt of a fatty acid having eight to twenty-two carbon atoms with a halogen substituted sulfonate of the general formula X R1 some wherein X is halogen and R1 and Me are as above indicated, in thepresence of formyl morpholine.

2. In the process of producing a wetting, sudsing and detergent agent of the general formula R-CO-ORr-SOaMe wherein X is halogen and R1 and Me are as above indicated, at a temperature not substantially above 175 C. and in the morpholine.

presence of formyl ing and detergent agent of the general formula R'CO'ORi-SOsMe where R-CO is the acyl radical of a fatty acid having eight to twenty-two carbon atoms, R1 is a radical selected from the group consisting of alkylene and hydroxy alkylene radicals having two to four carbon atoms, and Me is a metal forming a water-soluble salt, the steps which consist in condensing a metal salt of a fatty acid having eight to twenty-two carbon atoms with a halogen substituted sulfonate of the general formula X-RrSOsMe where X is halogen and R1 and Me are as above indicated, in the presence of formy1 morpholine, and-distilling ofithe formyl morpholine at a temperature not substantially higher than C 4. The process of claim 1 in which the halogen substituted sulfonate is a monochlorhydrin 'sulfonate.

,5. The process of claim 1 in which the fatty acid salt is sodium coconut oil soap and the halogen substituted sulfonate is moncchlorhydrin sodium sulfonate.

6. The process of claim 1 in which the fatty acid salt is sodium oleate and the halogen substituted sulfonate is monochlorh'ydrin sodium sulfonate.

7. The process of claim 1 in which the halogen substituted sulfonate is a beta methyl monochlorhydrin sulfonate.

8. The process of claim 1 in which the fatty acid salt is sodium coconut oil soap and the halogen substituted sulfonate is beta methyl monochlorhydrin sodium sulfonate.

4's ll BEVERLEY TUCKER; 

